Yan Chun-Na, Xu Lin, Liu Qing-Di, Zhang Wei, Jia Rui, Liu Cheng-Zhi, Wang Shuang-Shuang, Wang Li-Ping, Li Guang
College of Materials Science and Engineering, Liaocheng University, Liaocheng 252059, China.
College of Materials Science and Engineering, Qingdao University, Qingdao 266071, China.
Polymers (Basel). 2019 Jul 23;11(7):1228. doi: 10.3390/polym11071228.
Well-defined polymer brushes attached to nanoparticles offer an elegant opportunity for surface modification because of their excellent mechanical stability, functional versatility, high graft density as well as controllability of surface properties. This study aimed to prepare hybrid materials with good dispersion in different solvents, and to endow this material with certain fluorescence characteristics. Well-defined diblock copolymers poly (styrene)--poly (hydroxyethyl methyl acrylate)--poly (hydroxyethyl methyl acrylate- rhodamine B) grafted silica nanoparticles (SNPs--PS--PHEMA--PHEMA-RhB) hybrid materials were synthesized via surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). The SNPs surfaces were modified by 3-aminopropyltriethoxysilane (KH-550) firstly, then the initiators 2-Bromoisobutyryl bromide (BIBB) was attached to SNPs surfaces through the esterification of acyl bromide groups and amidogen groups. The synthetic initiators (SNPs-Br) were further used for the SI-ARGET ATRP of styrene (St), hydroxyethyl methyl acrylate (HEMA) and hydroxyethyl methyl acrylate-rhodamine B (HEMA-RhB). The results indicated that the SI-ARGET ATRP initiator had been immobilized onto SNPs surfaces, the Br atom have located at the end of the main polymer chains, and the polymerization process possessed the characteristic of controlled/"living" polymerization. The SNPs--PS--PHEMA--PHEMA-RhB hybrid materials show good fluorescence performance and good dispersion in water and EtOH but aggregated in THF. This study demonstrates that the SI-ARGET ATRP provided a unique way to tune the polymer brushes structure on silica nanoparticles surface and further broaden the application of SI-ARGET ATRP.
附着在纳米颗粒上的结构明确的聚合物刷，因其出色的机械稳定性、功能多样性、高接枝密度以及表面性质的可控性，为表面改性提供了一个绝佳的机会。本研究旨在制备在不同溶剂中具有良好分散性的杂化材料，并赋予该材料一定的荧光特性。通过电子转移活化剂再生原子转移自由基聚合（SI-ARGET ATRP）合成了结构明确的二嵌段共聚物聚（苯乙烯）-聚（甲基丙烯酸羟乙酯）-聚（甲基丙烯酸羟乙酯-罗丹明B）接枝二氧化硅纳米颗粒（SNPs-PS-PHEMA-PHEMA-RhB）杂化材料。首先用3-氨丙基三乙氧基硅烷（KH-550）对SNPs表面进行改性，然后通过酰溴基团与氨基的酯化反应将引发剂2-溴异丁酰溴（BIBB）附着在SNPs表面。合成的引发剂（SNPs-Br）进一步用于苯乙烯（St）、甲基丙烯酸羟乙酯（HEMA）和甲基丙烯酸羟乙酯-罗丹明B（HEMA-RhB）的SI-ARGET ATRP。结果表明，SI-ARGET ATRP引发剂已固定在SNPs表面，Br原子位于主聚合物链末端，聚合过程具有可控/“活性”聚合的特征。SNPs-PS-PHEMA-PHEMA-RhB杂化材料在水和乙醇中表现出良好的荧光性能和分散性，但在四氢呋喃中会聚集。本研究表明，SI-ARGET ATRP为调控二氧化硅纳米颗粒表面的聚合物刷结构提供了一种独特的方法，并进一步拓宽了SI-ARGET ATRP的应用范围。
